Catalytic activity of a dinuclear manganese complex (MnMeTACN) on the oxidation of ethyl linoleate

Oyman, Z.O.; Ming, Weihua; Linde, R. van der

doi:10.1016/j.apcata.2006.09.023

Cited by 23 publications

(23 citation statements)

References 25 publications

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“…The Mn-Me 3 TACN catalyst itself showed a low and slow conversion of EL towards hexanal as compared to Co II (2-EH) 2 . Upon addition of HMTT to [Mn IV,IV 2 (µ-O) 3 (Me 3 TACN) 2 ](PF 6 ) 2 , the reactivity was greatly enhanced, which has been linked to the earlier studies on enhanced formation of alkoxy radicals when HMTT was included in the formulation [26]. In the same paper, electrospray MS was also used to study the reactivity between [Mn IV,IV 2 (µ-O) 3 (Me 3 TACN) 2 ](PF 6 ) 2 and t BuOOH [26].…”

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 72%

“…Although one can most likely conclude, based on the studies [23,26] on the reactivity of [Mn IV,IV 2 (µ-O) 3 (Me 3 TACN) 2 ](PF 6 ) 2 with alkyd paints, that radical based autoxidation chemistry will be operative for the Mn-Me 3 TACN complexes or mixtures discussed in different patents, further detailed investigations would be needed to elucidate the nature of the catalytically active species involved in alkyd paint drying using different sources of Mn-Me 3 TACN and whether different sources of Mn-Me 3 TACN would lead to the same mechanistic pathways of radical-based alkyd resin curing.…”

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

“…Various new signals were observed that were assigned to mononuclear and dinuclear Mn III complexes. No further evidence using other spectroscopic techniques on the nature of these species was given in the paper, so the conclusions given should be treated with caution (mass spectrometry analyses on reactive intermediates metal complexes may lead to spurious results as oxidation, reduction or further reactions may occur in the spectrometer) [26]. The authors proposed that reaction of [Mn IV,IV 2 (µ-O) 3 2 ] 2+ complexes are also active to dry paint [27].…”

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

“…A continuation of the studies on the reactivity of [Mn IV,IV 2 (µ-O) 3 (Me 3 TACN) 2 ](PF 6 ) 2 towards ethyllineolate (EL) oxidation in the absence and presence of HMTT was carried out using head-space GC analyses for the determination of volatile reaction products (such as hexanal and heptanal) [26]. The Mn-Me 3 TACN catalyst itself showed a low and slow conversion of EL towards hexanal as compared to Co II (2-EH) 2 .…”

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

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Manganese and Iron Catalysts in Alkyd Paints and Coatings

Hage¹,

Böer²,

Maaijen³

2016

Inorganics

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Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model) alkyd curing using manganese and iron catalysts.

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Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 72%

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

Section: Manganese 147-triazacyclononane Catalystsmentioning

confidence: 99%

See 2 more Smart Citations

Manganese and Iron Catalysts in Alkyd Paints and Coatings

Hage¹,

Böer²,

Maaijen³

2016

Inorganics

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“…Some commercial paint formulations contain manganese carboxylate as a primary drier, even though these do not have the same performance as cobalt-based driers [3,4]. This has initiated a search to find alternatives for cobalt complexes as drying catalysts in alkyd paint [5][6][7][8][9][10]. Recently, our group reported on Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

Gorkum

Berding

Tooke

et al. 2007

Journal of Catalysis

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The activity of new manganese and iron complexes of dianionic tripodal ligands in the autoxidation of ethyl linoleate (EL) is reported. EL consumption rates were monitored using time-resolved FTIR and the degree of oligomerisation was determined by SEC. Almost all complexes showed the same trend in the autoxidation of EL. After a short induction time, the reaction started at a relatively high constant rate; later, this rate changes to a lower rate, which was again constant and on average was the same for all complexes studied. The observation that the autoxidation rate eventually became the same for all complexes can be explained with the assumption that a catalytic species was formed that was structurally similar for each complex. The crystal structure of a representative new complex, [Mn(papy)(acac)] (H 2 papy = N-(2-hydroxybenzyl)-N -(2-picolyl)-glycine; Hacac = acetylacetone), was elucidated, demonstrating a Jahn-Teller distorted octahedral geometry of the Mn(III) ion. To gain insight into the reaction mechanisms by which these manganese complexes react with peroxides, the reaction of [Mn(pppy)(dpm)] with alkyl hydroperoxides was studied using UV-vis and EPR spectroscopy (H 2 pppy = 2-[bis(2-hydroxybenzyl)aminomethyl]-pyridine; Hdpm = dipivaloylmethane). It is proposed that in a reaction of [Mn(pppy)(dpm)] with t-butyl hydroperoxide ( t BuOOH), the species [Mn(III)(pppy)(OH)( t BuOO · )] is formed. In analogy with the formation of that species, which is postulated to occur through a reduction to Mn(II), it is proposed that in the direct initiation reaction of EL with a manganese(III) complex, a 1 electron-1 proton transfer reaction leads to the formation of Mn(II) and an EL radical. Considering parameters such as autoxidation activity, complex solubility and ease of complex preparation, the compound [Mn(III)(tbpppy)(dpm)] (H 2 tbpppy = 2-[bis(2-hydroxy-3,5-di-tert-butylbenzyl) aminomethyl]pyridine) is expected to be the best potential alkyd paint drier.

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The Quest for Cobalt‐Free Alkyd Paint Driers

Böer¹,

Wesenhagen²,

Wenker³

et al. 2013

Eur J Inorg Chem

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Paint formulations, based either on organic solvents or on water, often contain alkyd resins that depend on catalysts for their oxidative curing. Cobalt carboxylates are the most widely used to date, but the use of these compounds is under pressure because classification as carcinogens under the REACh system is probable, and as a consequence there is great interest in the development of alternative driers to cobalt-based ones. A variety of manganese and iron carboxylates have been studied as paint drying catalysts in the last[a] Catexel BV, www.eurjic.org MICROREVIEW coating dries. Metal ions and complexes can facilitate these oxidation reactions and polymerisations. During the autooxidation of alkyd paints the unsaturated fatty acids react with molecular oxygen from the air to form -initiallyalkyl hydroperoxides (Scheme 1). [3,4] Subsequent decomposition of these alkyl hydroperoxides yields alkoxy and per-Johannes W. de Boer received his PhD in chemistry (2008) from the University of Groningen, the Netherlands, under the guidance of Prof. Ben L. Feringa and Dr. Ronald Hage and was awarded the Backer Prize by the Royal Dutch Chemical Society for his thesis on manganese-catalysed oxidation reactions. In 2007 he joined Rahu Catalytics, currently Catexel, where he works as Research Principal. His current research interests include the development of new oxidation catalysts and processes for a wide variety of (industrial) applications, focussing on manganese-and iron-catalysed activation of hydrogen peroxide and oxygen. Philana V. Wesenhagen gained her master's degree in chemistry at the University of Groningen in 2006 and joined the team of Rahu Catalytics from 2007 to 2009. After this she switched her fields of interest from chemistry to biotechnology and obtained a second master's degree, in cellular and molecular biotechnology at Wageningen University, in 2011. Currently she is doing her PhD at the Forschungszentrum in Jülich at the Institut für Bio-und Geowissenschaften. Erica C. M. Wenker gained a master's degree in chemistry (2010) at Leiden University, the Netherlands. During her master's she carried out mechanistic research on paint-drying catalysts at Rahu Catalytics. She is currently doing a PhD in coordination chemistry and catalysis under the guidance of Prof. Dr. Elisabeth Bouwman at Leiden University. Karin Maaijen obtained a bachelor's degree in chemistry in 2007 and a master's degree in chemistry and physics (2009) from Utrecht University (the Netherlands) with a major in inorganic chemistry and catalysis. In 2010 she joined Rahu Catalytics, currently Catexel, where she works as a Research Scientist on iron and manganese catalysts for various industrial applications. Franjo Gol gained a master's degree in chemistry and a Dr. rer. nat. in inorganic and organophosphorus chemistry at Wuppertal University. He has worked in the chemical industry for 26 years, initially on the development of water-borne binders for coatings for Herberts and then on binders, metal carboxylates and paint additives for Abshag...

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Catalytic activity of a dinuclear manganese complex (MnMeTACN) on the oxidation of ethyl linoleate

Cited by 23 publications

References 25 publications

Manganese and Iron Catalysts in Alkyd Paints and Coatings

Manganese and Iron Catalysts in Alkyd Paints and Coatings

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

The Quest for Cobalt‐Free Alkyd Paint Driers

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